CN1954797A - Compositions comprising polymeric emulsifiers and methods of using the same - Google Patents

Compositions comprising polymeric emulsifiers and methods of using the same Download PDF

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Publication number
CN1954797A
CN1954797A CNA200610142524XA CN200610142524A CN1954797A CN 1954797 A CN1954797 A CN 1954797A CN A200610142524X A CNA200610142524X A CN A200610142524XA CN 200610142524 A CN200610142524 A CN 200610142524A CN 1954797 A CN1954797 A CN 1954797A
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emulsion compositions
compositions
polymeric emulsifiers
skin
emulsion
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J·J·利布里兹
A·J·科斯
E·爱德华兹
D·伯西
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Johnson and Johnson Consumer Inc
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Johnson and Johnson Consumer Companies LLC
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/16—Emollients or protectives, e.g. against radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

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Abstract

Provided are oil-in-water sunscreen compositions comprising inorganic sunscreens and polymeric emulsifiers that are substantially free of hydrophobic modification, and methods of using the same.

Description

The compoistion and method of use that contains polymeric emulsifiers
Technical field
The present invention relates to contain the O/w emulsion of polymeric emulsifiers, more specifically relate to the O/w emulsion that contains polymeric emulsifiers and opacifier of the unique combination that demonstrates sun-proof, anti-flushing and/or low stimulus quality.
Background technology
Fully confirmer's skin to daylight and contain the radiating artificial light sensitivity that wavelength is about the 290-400 nanometer.The light radiation that wavelength is about the 290-320 nanometer is called as the UV-B ray, and it can cause skin burn and erythema, occurs thereby influence the crude palm brown.The UV-A ray that wavelength is about the 320-400 nanometer can also cause skin damage easily with skin tanning, especially to sensitive skin or be exposed to skin under the solar irradiation continuously.The UV-A ray especially can make skin follow the string and wrinkle occur, causes the skin premature aging.They can impel and erythema reaction (erythmal reaction) occurs or strengthen this reaction in some individuality, and even can cause phototoxic reaction or photoallergy.Therefore, the applicant thinks, needs UV-A and UV-B ray on the filtering skin, for example by apply the topical composition that can block this harmful radiation and prevent photic damage on skin.
The applicant thinks, the external sunscreen composition should be effectively and efficiently for skin blocks the UV radiation, and should have good aesthetic characteristic (for example, no greasy feeling and can not make skin whitening) and/or relatively low to the stimulation of skin and eyes.The zest and the sensitivity that when consideration is used for baby or child with these products, especially need to reduce the opacifier product.In addition, also need the opacifier can the waterproof antiperspirant in many cases, thereby need not to smear again continually.The applicant thinks that conventional sunscreen composition can not make up these characteristics ideally.
For example, some conventional sunscreen composition adopt inorganic sunscreen, as titanium dioxide and zinc oxide, to improve the mildness of opacifier prescription.Yet many this inorganic sunscreen prescriptions have met with aesthetic problem when reducing zest and sensitivity, as make skin whitening.In addition, for required SPF and good phase stability are provided, inorganic sunscreen is made into water-in-oil emulsion usually, considers that from aesthstic angle this is not preferred.
Made other effort of preparation sunscreen composition, comprising, for example, the United States Patent (USP) 5 of product described in the following patent documentation: Lukenbach etc., 980,871 and 6,540,986B2 (relates to and contains inorganic sunscreen, anion emulsifier, the inorganic sunscreen system of oily components and at least a softening agent), the U.S. Patent application 2004/0071641A1 (relate to and use amphiphilic polymers and the insoluble inorganic and/or organic opacifier that contains at least one ethylenically unsaturated monomers, above-mentioned monomer comprises sulfo group and contains at least one hydrophilic segment) of U.S. Patent application 2004/0067208 A1 of Lennon etc. (relating to two oligomers that use the polyolefin derivative contain at least one polarity part or the metal-oxide UV-blocker of polymer and effective dose) and Boutelet etc.Yet the applicant thinks, though this system can make the compositions with enough SPF that satisfies certain purposes, they also can lack in sunscreen composition required anti-washability, aesthetic characteristic and/or the low irritant one or more.
Therefore, still need to provide waterproof, antiperspirant, easy to use, smear invisible (can not turn white), can not dyeing, non-greasy and to skin and the low anti-UVA that stimulates of eyes and effective preventing coating protection of UVB ray.
Summary of the invention
The applicant is unexpected to be found, inorganic sunscreen can obtain a kind of sunscreen composition with some polymeric emulsifiers combination, compares conventional opacifier, and this compositions is perfect and shockingly combine with sun-proof, anti-flushing and low stimulus quality.Therefore, one aspect of the present invention relates to the oil-in-water sunscreen composition that contains inorganic sunscreen and be substantially free of the polymeric emulsifiers of hydrophobic modification, and this sunscreen composition is substantially free of monomer emulsifying agent.
Another aspect of the present invention relates to the oil-in-water sunscreen composition that contains inorganic sunscreen and be substantially free of the polymeric emulsifiers of hydrophobic modification, and this sunscreen composition is substantially free of organic opacifier.
The applicant finds that also some compositions that contains the inorganic sunscreen that comprises titanium dioxide and zinc oxide simultaneously not only has gratifying SPF, aesthetic feeling and mildness, and shockingly anti-flushing.Therefore, another aspect of the present invention relates to the oil-in-water sunscreen composition that contains inorganic sunscreen and be substantially free of the polymeric emulsifiers of hydrophobic modification, and described inorganic sunscreen comprises the mixture of titanium dioxide and zinc oxide.
Another aspect of the present invention relates to the method that protection skin exempts from photic damage, and this method is included in coating compositions of the present invention on the skin.
DESCRIPTION OF THE PREFERRED
The applicant is unexpected to find that the hydrophobically modified polymeric emulsifiers that is substantially free of hydrophobic modification can be combined to form the compositions that has overcome the one or more shortcomings of conventional sunscreen composition with inorganic sunscreen.That is to say that the applicant finds, compares conventional emulsion compositions, emulsion compositions of the present invention has the higher relatively solar protection factor (SPF) and higher relatively anti-washability, good aesthetic, low skin irritability and/or low eye irritation.
Specifically; the applicant has tested the solar protection factor (SPF) of the present composition by " the SPF test " described in detail below; as be proficient in those skilled in the art and understand, higher spf value represents that compositions can protect skin to exempt from the adverse effect of ultraviolet radiation better.The applicant is unexpected to be found, compares conventional Comparative composition, and compositions display of the present invention goes out unusual high spf value.For example, in certain embodiments, the spf value of the present composition is at least about 10 or higher, preferably is at least about 12 or higher, more preferably is at least about 15 or higher, preferably is at least about 20 or higher again.In the embodiment that some is more preferably, the spf value of the present composition is at least about 25 or higher, preferably is at least about 30 or higher, more preferably is at least about 45 or higher, is more preferably 60 or higher.In some preferred embodiment, the spf value of the Comparative composition that this spf value may be outer than the scope of the invention exceeds at least about 2 times, preferably at least about 3 times, more preferably at least about 4 times or higher.
The applicant has also measured the anti-washability of compositions that the present invention requires with the measurement method of describing in detail below of anti-flushing the (Rinse Resistance Measurement), wherein measured and soak 40 minutes (%R in water 40) and 80 minutes (%R 80) residue SPF in back accounts for the percentage ratio of initial SPF, and, be proficient in one of skill in the art will appreciate that be percentage ratio (%R 40/ %R 80) the anti-washability of high more then said composition is good more.The applicant finds, compares other sunscreen composition, and the present composition may have unusual high %R 40And %R 80Value.For example, in certain embodiments, the %R40 of the present composition is at least about 80%, preferably is at least about 85%, more preferably is at least about 90%, more preferably is at least about 95%, more preferably is at least about 98%, preferably is about 100% again.In addition, in certain embodiments, the %R of the present composition 80Be at least about 80%, preferably be at least about 85%, more preferably be at least about 90%, more preferably be at least about 95%, more preferably be at least about 98%.In some preferred embodiment, the percentage ratio (%R of the Comparative composition that its percentage ratio may be outer than the scope of the invention 40/ %R 80) exceed at least about 1.2 times, preferably at least about 1.4 times, more preferably from about 1.6 times, more preferably from about 2 times or higher.
In addition, the applicant has also measured the zest of the present composition by eye twinge test described below (Ocular Sting Test).The applicant finds that the present composition is gentle relatively to eyes, and preferably the zest to eyes is starkly lower than Comparative composition.
In particularly preferred embodiments, the applicant finds, inorganic sunscreen can be mixed with polymeric emulsifiers of the present invention to obtain SPF and be at least 10, and preferably at least 15, %R 40Value is at least about 90%, preferably is about 95%, %R 80Value is at least about 90%, preferably is about 95%, in addition to the oil-in-water sunscreen composition of eyes gentleness.
Any suitable inorganic sunscreen all can be used for compositions of the present invention.The applicant thinks, in certain embodiments, inorganic sunscreen should can be dispersed in the water, its particle diameter is about 0.01-500 micron, preferred about 0.1-500 micron, more preferably from about 0.5-300 micron, more preferably from about 1.0-200 micron, 1-50 micron more preferably from about, and should in UV-A and/or UV-B zone, have activity (absorbent).In some preferred embodiment, inorganic sunscreen comprise diameter less than 40 microns, preferably less than 1 micron, the subparticle of 0.1-0.5 micron more preferably from about.In certain embodiments, inorganic sunscreen can have or not have comprise one or more hydrophobic parts face coat (for example, silicone compounds and aluminium stearate, fatty acid, fatty ester coating, hydrophobic surface is modified as the finishing from some organosilan, or the like), this hydrophobic part can be eliminated the hydrophilic nmature of inorganic sunscreen.The unrestricted example that is suitable for inorganic sunscreen of the present invention comprises: metal-oxide such as ferrum oxide, titanium dioxide, zirconium oxide, zinc oxide, transition metal oxide or other oxide pigment, various forms of silicon dioxide, aluminosilicate, carbonate, and wherein two or more combination, or the like.In certain preferred aspects, titanium dioxide, zinc oxide and their combination are preferred especially.
The applicant thinks that in certain embodiments, the combination of titanium dioxide and zinc oxide can be used for the present invention to obtain to have the compositions of high unusually anti-washability.Therefore, some particularly preferred inorganic sunscreen of the present invention comprises the combination of titanium dioxide and zinc oxide.
The inorganic sunscreen of any appropriate amount all can be used for compositions of the present invention.In certain embodiments, the present composition contains the 0.01-50 weight % that has an appointment, preferably about 0.1-35 weight %, one or more inorganic sunscreen of 0.1-20 weight % more preferably from about.Except as otherwise noted, weight % represents that active component weight accounts for the percentage ratio of compositions gross weight in entire description.
According to the present invention, can use any suitable polymeric emulsifiers that is substantially free of hydrophobic modification.Term " is substantially free of hydrophobic modification " and contains in the ordinary representation polymeric emulsifiers in the text the mole percent of hydrophobic part of 4 above covalent bond carbon atom together less than 1 weight %, preferably less than 0.5 weight %, be more preferably less than 0.1 weight %, be more preferably less than 0.01 weight %.In the literary composition, mole percent is that the molal quantity that contains the hydrophobic part of 4 above covalent bond carbon atom together in the polymer multiply by 100 again divided by polymer monomer unit total mole number.
In some preferred embodiment, the applicant thinks and should use one or more to be substantially free of the polymeric emulsifiers of hydrophobic modification, can between oil phase and water, form stable emulsion like this, the SPF of storage stability and/or raising compositions is provided for the compositions that adds polymeric emulsifiers.In addition, some preferred polymeric emulsifiers comprises the phase stable emulsion that those are water miscible and can form mineral oil in water, preferred stable is at least about for 1 week, more preferably at least about 1 month compositions.(in the literary composition, can be formed in the settled solution (precipitation or unstable does not mutually take place) of stablizing 48 hours under the room temperature in deionized water then this material is defined as " water miscible " if certain material of 0.5 weight % added.) some preferred polymeric emulsifiers of the present invention is to the salt sensitivity, promptly their dissolubility in water usually can violent decline when (as appearing at the electrolyte of skin surface usually) there being electrolyte.If polymeric emulsifiers is lost it and is kept the ability of water-soluble liquid stable then be defined as " to the salt sensitivity " when adding sodium chloride.Specifically, if add 3% sodium chloride in the deionized water homogeneous solution of (activity) polymeric emulsifiers 1%, the polymeric emulsifiers of " to the salt sensitivity " will be separated and/or viscosity-modifying 30% or above (measuring with the Brookfield viscometer of 12rpm rotation with the LVT2 main shaft).
Polymeric emulsifiers of the present invention can have any suitable molecular weight.In certain embodiments of the invention, the weight average molecular weight of polymeric emulsifiers should be greater than about 100,000, more preferably greater than about 250,000, is preferably greater than about 500,000 again.
Polymeric emulsifiers of the present invention can comprise one or more monomers (being that polymeric emulsifiers can be homopolymer, copolymer, terpolymer etc.).Comprise in two or more monomeric embodiments that condense together at polymer, this two or more monomers can have any suitable ratio.In a preferred embodiment, polymeric emulsifiers can be used following chemical formulation:
In the formula, a is 0-0.99, and b is 0.01-1, and a+b=1, R 1And R 2Identical or different, all be straight chain, side chain or the loop section that contains the continuous carbon atom of 4 above covalency.
In a preferred embodiment, R 1Can be represented by the formula:
X-Y-Z -M +；
In the formula, X is selected from-COO-,-OCO-,-CONH-and-NHCO-; Y is straight chain, side chain or ring-type (C 1-4) alkyl; Z is-COO -,-SO 3 -,-SO 4 -,-PO 3 -With-PO 4 -Deng the anionic functional group; M +Be Li +, Na +Or K +Deng metal ion or ammonium equilibrium ion NH 4 +
In a preferred embodiment of the invention, X is NHCO-, and Z is-SO 3 -, Y is a methyl, i.e. R 1It is acrylamide alkyl sulfonic acid salt (AMPS) part.
In a further preferred embodiment, R 2Can be represented by the formula:
X-Y-Z -M +；
In the formula, X, Y, Z and M can be selected from and above be R 1Those parts of definition.
In some other preferred embodiment, R 2Expression comprises nonionic straight chain, side chain or the cyclic group of 0-4 covalent bond carbon atom chain.For example, R 2Can comprise annulus, as contain the heterocycle of carbon, nitrogen, oxygen or its combination.
In some other preferred embodiment of the present invention, R 1Be the AMPS part, R 2Expression contains 0-4 the heteroatomic nonionic straight chain, side chain or the cyclic group that are selected from nitrogen or oxygen.
Polymeric emulsifiers can exist by various forms, comprises atactic polymer, block polymer, star polymer, graft polymers etc.Famous can include but not limited to by the polymeric emulsifiers that is substantially free of hydrophobic modification that commerce is buied: the acrylamide alkyl sulfonic acid of buying from Clariant with trade name Aristoflex  AVC and the copolymer of ring N-vinyl carboxylic acid amides; The AMPS homopolymer; as with trade name Granthix APP from Grant Industries; the homopolymer of the acrylamide alkyl sulfonic acid of Inc. buying provides the mixture of polyacrylamide dimethyl taurine ammonium (AmmoniumPolyacryloyldimethyltaurate) and 2-Methylpentadecane and polyoxyethylene sorbitan monoleate.
The polymeric emulsifiers that is substantially free of hydrophobic modification of any appropriate amount can be used for compositions of the present invention.In some preferred embodiment, compositions of the present invention contains the polymeric emulsifiers that is at least about 0.3 weight %.In the embodiment that some is more preferably, the present composition contains, for example about 0.3-3%, about 0.3-2% and this polymeric emulsifiers of about 0.3-1%.
According to some embodiment, the present composition also contains one or more wetting agents.Term " wetting agent " refer in the text to have at least one sulfonate groups (part) and at least one alkali can in and the anion surfactant of hydroxy-acid group (part), it helps compositions wet substrates of the present invention and makes the water-repelling agent of compositions be retained in (for example, by avoiding the water-repelling agent reemulsification) in the substrate as wetting agent.The non-limiting ion of suitable wetting agent comprises the sulfosuccinate class, as laureth-(1-4) sulfosuccinate disodium, 2-Sulfosuccinic acid ethylhexyl sodium, 2-sulfolauric acid methyl ester sodium salt etc.; Hydroxyethylsulfonic acid. esters (isethiones) is as cocos nucifera oil acyl hydroxyethyl sulfonate etc.; And the sulfoacetic acid esters, as lauryl alcohol sulfoacetic acid ester sodium salt etc.Various these type of wetting agents can be buied from various sources, comprise McIntyre Group Limited (the sulfosuccinate disodium of the laureth of selling with trade name MACKANATE EL-(1-4), 2-Sulfosuccinic acid ethylhexyl sodium with trade name MACKANATE DOS 70 sales), Stepan Company is (with the 2-sulfolauric acid methyl ester sodium salt of trade name ALPHA STEP PC 48 sales, the lauryl alcohol sulfoacetic acid ester sodium salt of selling with trade name LANTHANOL LAL) and Clariant Corporation (the cocos nucifera oil acyl hydroxyethyl sulfonate of selling with trade name HOSTAPON SCI 85).
The wetting agent of any appropriate amount can be used for compositions of the present invention.In certain embodiments, the present composition contains more than 0 to about 1 weight % wetting agent, is preferably about 0.1-1, and more preferably about 0.1-0.5 is preferably the active wetting agent of about 0.3-0.5 weight % again.
In some preferred embodiment, compositions of the present invention is substantially free of monomer emulsifying agent.The compositions that " is substantially free of term monomer emulsifying agent " and refers in the text contains less than about 1.0%, preferably less than about 0.5%, be more preferably less than about 0.1%, more preferably less than about 0.01%, perhaps less than about 0.001% monomer emulsifying agent.Term " monomer surface-active emulsifiers " is at any or multiple non-polymeric surfactant that refers to except that above-mentioned " wetting agent ", and it can be used to oil is emulsified into O/w emulsion (water soluble).Described monomer surfactant can be anion, both sexes, cation or non-ionic surface active agent.
In some preferred embodiment, compositions of the present invention is substantially free of organic opacifier.Term " is substantially free of organic opacifier " and is referring to that compositions contains less than about 1.0%, preferably less than about 0.5%, be more preferably less than about 0.1%, again preferably less than about 0.01%, perhaps less than about 0.001% organic opacifier, organic opacifier can be selected from ethylhexyl salicylate, ethylhexyl methoxy cinnamate, octocrilene, Phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5,4 methyl benzylidene camphor sulfonic acid (4-methylbenzylidene camphor), the Terephthalidene Dicamphor Sulfonic Acid, phenyl bisbenzimidazole tetrasulfonic acid disodium, 2,4,6-three (diisobutyl 4 '-the aminobenzene methylene malonate)-the s-triazine, different triazine (anisotriazine), hydrazoic acid Octyl Nitrite (ethylhexyl triazonc), diethylhexyl butyryl triazinone (diethylhexyl butamido triazone), methylene dibenzo triazolyl tetramethyl butyl phenol, the drometrizole trisiloxanes, 1,1 '-dicarboxyl (2,2 '-dimethyl propyl)-4, the 4-diphenyl diethylene, their mixture, or the like.
Compositions of the present invention also can contain additive or other normally used material of any kind of.For example, the present composition can contain dyestuff, essence and skin care compositions and methods other functional components commonly used, as long as they can not destroy the phase stability of personal care composition.Usually, for keeping phase stability, (for example, the ionizing part beyond the wetting agent) level is maintained at or maintains substantially relatively low level to electrolyte, and about 2% as less than total composition is as less than about 0.5% of total composition.
The present composition should be made into to stablize the O/w emulsion of preservation, and it can not lose phase stability or quilt " destruction " when standard conditions (22 ℃, 50% relative humidity) are preserved 1 week or longer time down after making.
The present composition can have any suitable pH to improve storage stability and to make stimulation minimum to skin and eyes.In one embodiment of the invention, pH is about 4.0-9.0, is more preferably 5.5-7.5.In addition, the present composition can have any suitable stability and raising the joyful sense when being coated on skin of viscosity to improve compositions.
The applicant thinks that compositions of the present invention can the useful use of various methods of application.For example, in some preferred embodiment, the present composition is made into or is used for external personal care composition and/or product, as recreational sunlight care product, daily wetting agent, color make-up and other skin care compositions and methods etc.
In another embodiment of the invention, described personal care composition is used as wetting agent and is coated on skin to reduce the steam loss of skin.In another embodiment of the invention, described personal care composition is applied to face again.
In some preferred embodiment, the described personal nursing present composition should be coated on skin and keep a period of time on skin, 30 minutes to about 24 hours according to appointment, during do not wash with suds.
Embodiment
Embodiment 1-8
Following examples are as the illustration of the present composition, yet they do not limit scope of invention described here.
Prepared 5 kinds of personal care compositions, embodiment 1,2,5,6 and 8, and they are consistent with embodiment of the present invention.Also 3 kinds of Comparative composition have been prepared, Comparative Examples 3,4 and 7 according to the description here.The group component that provides in this process is expressed as the parts by weight of per 100 parts of final personal care compositions.
Be prepared as follows the emulsion system shown in embodiment 1,2,5 and 6:
Add three (3.0) parts of glycerol after the water of deal shown in the table 1 deducted 15.0 parts, solution stirring to evenly, is added 0.3 part of parabens and is heated to 60-65 ℃ and dissolve up to parabens.In this solution, add 0.75 part of ammonium acryloyldime-thyltaurate// VP copolymer (ammonium acryloyldimethyltaurate/VPCopolymer) and mix up to solution evenly, then this solution is placed phasing (1 solution mutually) at 60-65 ℃.In another container, 7.0 parts of mineral oil and 3.75 parts of capric acid/Trivent OCGs are heated with stirring to 60-65 ℃.In embodiment 1 and 2, add 4.5 parts of titanium dioxide and mixing until dispersion.In embodiment 5 and 6, add 4.0 parts of zinc oxide and mixing until dispersion, maintain 60-65 ℃ then.The limit is stirred the limit rapidly gained solution is added above-mentioned solution (mutually 1 solution) then.Stop to heat the back and add 15 parts of water coolings, continue stirring and get evenly up to solution becomes.In embodiment 5 and 6, add 4.5 parts of titanium dioxide and uniform homogeneous blend.In embodiment 2 and 6, add 0.65 and 0.10 part of 2-sulfolauric acid methyl ester sodium salt and 2-sulfolauric acid disodium respectively and with the mixture homogenizing.Mixture is cooled to 35 ℃, in embodiment 6, adds 1.0 parts of phenoxyethanol and stirring up to dissolving fully.In embodiment 1 and 2, the words that need can transfer to 5.5-6.5 with pH.In embodiment 5 and 6 (embodiment that comprises zinc oxide), the words that need can transfer to 7.0-8.0 with pH.
Be prepared as follows the emulsion system shown in embodiment 3 and 4:
Add 3.0 parts of glycerol after the water of deal shown in the table 1 deducted 15.0 parts, with solution stirring to evenly.Add 0.75 part of hydroxyethyl-cellulose and be heated to 60-65 ℃ while stirring and dissolve fully, then this solution is placed phasing (2 solution mutually) at 60-65 ℃ up to hydroxyethyl-cellulose.In another container, 7.0 parts of mineral oil and 3.75 parts of capric acid/Trivent OCGs are heated with stirring to 60-65 ℃.Add 1.56 parts of laureth-4,0.44 part stearyl alcohol polyethers-21 and 4.0 part spermol and mixing up to melting and becoming even.Add 4.5 parts of titanium dioxide and mix until dispersion, maintain 60-65 ℃ then, the limit is stirred the limit rapidly this solution is added above-mentioned solution (2 solution mutually) then.Stop to heat the back and add 15 parts of water coolings, continue stirring and get evenly up to solution becomes.In embodiment 4, add 0.65 part of 2-sulfolauric acid methyl ester sodium salt and 2-sulfolauric acid disodium and be mixed to even.Mixture is cooled to 35 ℃, adds 0.3 part of parabens and phenoxyethanol and stirring up to dissolving fully.The words that need can transfer to 5.5-6.5 with pH.
Be prepared as follows the emulsion system shown in the embodiment 7:
Add 3.0 parts of glycerol after the water of deal shown in the table 1 deducted 15.0 parts.With the gained solution stirring extremely evenly.Add 0.30 part of parabens and be heated to 60-65 ℃ and dissolve up to parabens.In this solution, add 0.75 part of hydroxyethyl-cellulose and mix and dissolve, then this solution is placed phasing (3 solution mutually) at 60-65 ℃ up to hydroxyethyl-cellulose.In another container, 7.0 parts of mineral oil and 3.75 parts of capric acid/Trivent OCGs are heated with stirring to 60-65 ℃.Add 1.56 parts of laureth-4,0.44 part stearyl alcohol polyethers-21 and 4.0 part spermol and mix and become even up to fusion and mixture.In this mixture, add 4.0 parts of zinc oxide and mixing until dispersion, maintain 60-65 ℃ then.The limit is stirred the limit rapidly this solution is added above-mentioned solution (mutually 3 solution) then.Stopping to heat the back adds 4.5 parts of titanium dioxide and is mixed to homodisperse.In this mixture, add 15.0 parts of water coolings, continue to mix getting evenly up to solution becomes.Mixture is cooled to 30-35 ℃ then.The words that need can transfer to 7.0-8.0 with pH.
Be prepared as follows the emulsion system shown in the embodiment 8:
Add 3.0 parts of glycerol after the water of deal shown in the table 1 deducted 15.0 parts and with solution stirring to evenly.Add 0.3 part of parabens and be heated to 60-65 ℃ and dissolve up to parabens.Add 2.05 parts of 2-Methylpentadecanes, polyacrylamide dimethyl taurine ammonium and polyoxyethylene sorbitan monoleate therein and mix and get evenly up to solution becomes.Then this solution is placed phasing (4 solution mutually) at 60-65 ℃.In another container, 7.0 parts of mineral oil and 3.75 parts of capric acid/Trivent OCGs are heated with stirring to 60-65 ℃.Add 4.5 parts of zinc oxide and mix until dispersion in this mixture, maintain 60-65 ℃ then, the limit is stirred the limit rapidly this solution is added above-mentioned solution (4 solution mutually) then.Stop to heat the back and add 15.0 parts of water coolings, continue to mix getting evenly up to solution becomes.Mixture is cooled to 30-35 ℃ then.The words that need can transfer to 5.5-6.5 with pH.
Table 1
The INCI name Embodiment 1 Embodiment 2 Comparative Examples 3 Comparative Examples 4 Embodiment 5 Embodiment 6 Comparative Examples 7 Embodiment 8
Ammonium acryloyldime-thyltaurate// VP copolymer 0.75 0.75 0.75 0.75
2-Methylpentadecane (with) polyacrylamide dimethyl taurine ammonium (with) polyoxyethylene sorbitan monoleate 2.05
Glycerol 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Titanium dioxide (with) aluminium stearate (with) aluminium hydroxide 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50
Zinc oxide 4.00 4.00 4.00
Mineral oil 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00
Capric acid/Trivent OCG 3.75 3.75 3.75 3.75 3.75 3.75 3.75 3.75
Spermol 4.00 4.00 2.00
Hydroxyethyl-cellulose 0.75 0.75 0.38
Laureth-4 1.56 1.56 1.56
Stearyl alcohol polyethers-21 0.44 0.44 0.44
2-sulfolauric acid methyl ester sodium salt 2-sulfolauric acid disodium 0.65 0.65 0.10
Methyl parahydroxybenzoate (with) ethylparaben (with) propyl p-hydroxybenzoate (with) butyl p-hydroxybenzoate 0.30 0.30 0.30 0.30 0.30
Methyl parahydroxybenzoate (with) ethylparaben (with) propyl p-hydroxybenzoate 0.30
Phenoxyethanol 1.00
Methyl parahydroxybenzoate (with) ethylparaben (with) propyl p-hydroxybenzoate (with) butyl p-hydroxybenzoate (with) phenoxyethanol 0.30 0.30
Sodium hydroxide Capacity Capacity Capacity Capacity Capacity Capacity Capacity Capacity
Citric acid Capacity Capacity Capacity Capacity Capacity Capacity Capacity Capacity
Water 80.70 80.05 74.70 74.05 76.70 75.05 73.07 79.40
SPF measures
Adopt Labsphere UV transmittance analyser to determine external SPF scoring.The substrate of adopting is the commodity VitroSkin by name available from IMS test group Can simulating human the artificial skin test substrate of form, pH, critical surface tension and ionic strength of skin, and with product with 2mg/cm 2Coating density be used for this substrate.Launch the spectral scan of light (or absorbing light) at the ultraviolet region of 250-450 nanometer.Adopt transmittance scanning and solar spectrum irradiancy and CIE erythema effect spectrum to calculate external SPF automatically then.To at least 5 spf values of each embodiment record, their meansigma methods is shown in following table 2.
Table 2.SPF measurement result:
Table-2
Embodiment Spf value
Embodiment 1 22.52
Embodiment 2 13.57
Embodiment 3 6.61
Embodiment 4 6.12
Embodiment 5 26.71
Embodiment 6 24.77
Embodiment 7 9.31
Embodiment 8 15.69
Embodiment 9 and 10
Below two embodiment also be in order to set forth compositions of the present invention, yet they do not limit scope of invention described here.
Prepared 2 kinds of personal care compositions, embodiment 9 and 10, they are consistent with embodiment of the present invention.
Be prepared as follows the emulsion system shown in embodiment 9 and 10:
Add 3.0 parts of glycerol after the water of deal shown in the table 1 deducted 15.0 parts, solution stirring to evenly, is added 0.3 part of parabens and is heated to 60-65 ℃ and dissolve up to parabens.In this mixture, add 0.75 part of ammonium acryloyldime-thyltaurate// VP copolymer and mix up to solution evenly, then this solution is placed phasing (1 solution mutually) at 60-65 ℃.In another container, 7.0 parts of mineral oil and 3.75 parts of capric acid/Trivent OCGs are heated with stirring to 60-65 ℃.In embodiment 9, add 4.5 parts of titanium dioxide and mixing until dispersion.In embodiment 10, add 4.5 parts of titanium dioxide and 2.0 parts of zinc oxide and mix until dispersion, maintain 60-65 ℃ then.The limit is stirred the limit rapidly gained solution is added above-mentioned solution (mutually 1 solution) then.Stop to heat the back and add 15 parts of water coolings, continue stirring and get evenly up to solution becomes.When reaching 25-30 ℃, temperature adds 1 part of phenoxyethanol.In embodiment 9, the words that need can transfer to 5.5-6.5 with pH.In embodiment 10, with material homogenizing 5 minutes on base, the words that need can transfer to 7.0-8.0 with pH.
Table-3
The INCI name Embodiment 9 Embodiment 10
Ammonium acryloyldime-thyltaurate// VP copolymer 0.75 0.75
Glycerol 3.00 3.00
Titanium dioxide (with) aluminium stearate (with) aluminium hydroxide 4.50 4.50
Zinc oxide 2.00
Mineral oil 7.00 7.00
Capric acid/Trivent OCG 3.75 3.75
Spermol
Methyl parahydroxybenzoate (with) ethylparaben (with) propyl p-hydroxybenzoate (with) butyl p-hydroxybenzoate 0.30 0.30
Phenoxyethanol 1.00 1.00
Sodium hydroxide Capacity Capacity
Citric acid Capacity Capacity
Water 80.70 80.05
The measurement method of anti-the flushing
Adopt Labsphere UV transmittance analyser, the percentage that accounts for initial SPF by definite flushing after 40 minutes and 80 minutes is recently estimated anti-washability.Used substrate is to remove corium and with the fresh Corium Gallus domesticus of 96% ethanol rinsing.4 microlitre products are coated on the skin samples of 16 millimeters of diameters and make its dry 15 minutes.The spectral scan of launching light (or absorbing light) at the ultraviolet region of 250-450 nanometer is to obtain initial external spf value.
Then skin samples was soaked 40 and 80 minutes in 19 premium on currency are bathed, do not stir.From water-bath, take out skin samples after stipulated time and air drying 20 minutes.Dry back is measured the external SPF after the flushing and is calculated the percentage ratio that accounts for initial SPF.This test triplicate is to obtain the sample size of each test 4.External SPF after the flushing be multiply by 100 percentage ratios that obtain accounting for initial SPF again divided by initial SPF.Write down the result of embodiment 9 and 10 and be shown in following table 4.
The result of table 4. wash off resistance test:
Table-4
Embodiment Account for the percentage ratio (%R of initial SPF 40) 40 minutes Account for the percentage ratio (%R of initial SPF 80) 80 minutes
Embodiment 9 85 84
Embodiment 10 100 98
Eye twinge test:
Adopt double blinding, at random, 2 yuan of (two cell) development tests designs, 1 about 38 ℃ sample of temperature is splashed in eye of experimenter.Each sample is adopted a new disposable sterilized eyedropper, and just abandon behind eye of experimenter being used for.All drip medicine and are undertaken by researcher or trained technical staff.
After dripping medicine, require the experimenter to adopt the sensation of pricking divided rank to eyes of following standard in 30 seconds or in the short as far as possible time to feeling:
Twinge
0=is in normal range
The 1=gentleness, very slight
2=is medium
3=is serious
Drip behind the medicine and to require the sensation of pricking divided rank to eyes of experimenter in 15 minutes and 60 minutes again feeling.
Write down the result of embodiment 9 and 10 and be shown in following table 5.
The result of table 5. human eye twinge test:
Table-5
Embodiment % eye twinge value *(embodiment vs contrast)
Embodiment 9 10
Embodiment 10 13
*Table 5 is expressed as about the result of eye twinge and finds that each embodiment causes twinge to their eyes experimenter's contrast is when giving to feel when their eyes contrast (being sterile distilled water) experimenter's the weighting percent of twinge.In other words, experimenter's weighting percent can calculate with following formula:
Wherein, X is in the summation literary composition of [(experimenter's number that given strength criterion is responded) (selected strength criterion)], if the % eye twinge value of this compositions is less than 20% then be considered to " to the eyes gentleness ".

Claims (22)

1. an O/w emulsion compositions that contains inorganic sunscreen and be substantially free of the polymeric emulsifiers of hydrophobic modification is characterized in that described emulsion compositions is substantially free of monomer emulsifying agent.
2. emulsion compositions as claimed in claim 1 is characterized in that its spf value is at least about 15.
3. emulsion compositions as claimed in claim 2 is characterized in that its spf value is at least about 20.
4. emulsion compositions as claimed in claim 1 is characterized in that, its %R 40At least about 90%.
5. emulsion compositions as claimed in claim 1 is characterized in that, its %R 40At least about 95%.
6. emulsion compositions as claimed in claim 1 is characterized in that, its %R 80At least about 90%.
7. emulsion compositions as claimed in claim 1 is characterized in that, its %R 80At least about 95%.
8. emulsion compositions as claimed in claim 1 is characterized in that described compositions is to the eyes gentleness.
9. emulsion compositions as claimed in claim 1 is characterized in that, described inorganic sunscreen is selected from metal-oxide, silicon dioxide, aluminosilicate, carbonate and wherein two or more combination.
10. emulsion compositions as claimed in claim 9 is characterized in that, described inorganic sunscreen is selected from titanium dioxide, zinc oxide and their combination.
11. emulsion compositions as claimed in claim 10 is characterized in that, described inorganic sunscreen comprises the combination of titanium dioxide and zinc oxide.
12. emulsion compositions as claimed in claim 1 is characterized in that, described polymeric emulsifiers has following structural formula:
Figure A2006101425240002C1
In the formula,
A is about 0-0.99, and b is about 0.01-1, and a+b=1, R 1And R 2Identical or different, for having the part of following formula: X-Y-Z -M +, wherein X be selected from following part :-COO-,-OCO-,-CONH-and-NHCO-; Y is straight chain, side chain or ring-type (C 1-4) alkyl; Z is selected from-COO -,-SO 3 -,-SO 4 -,-PO 3 -With-PO 4 -The anionic functional group; M +Be selected from Li +, Na +, K +And NH 4 +
13. emulsion compositions as claimed in claim 1 is characterized in that, described polymeric emulsifiers is the copolymer of acrylamide alkyl sulfonic acid and ring N-vinyl carboxylic acid amides.
14. emulsion compositions as claimed in claim 1 is characterized in that, described polymeric emulsifiers is the AMPS homopolymer.
15. one kind contains inorganic sunscreen and is substantially free of the O/w emulsion compositions of the polymeric emulsifiers of hydrophobic modification, described emulsion compositions is substantially free of monomer emulsifying agent and to the eyes gentleness, and its spf value is at least about 15, %R 40At least about 90%, %R 80At least about 90%
16. emulsion compositions as claimed in claim 15 is characterized in that, its spf value is at least about 20.
17. emulsion compositions as claimed in claim 15 is characterized in that, its %R 40At least about 95%.
18. emulsion compositions as claimed in claim 17 is characterized in that, its %R 80At least about 95%.
19. emulsion compositions as claimed in claim 15, it is characterized in that, described inorganic sunscreen is selected from titanium dioxide, zinc oxide and their combination, and described polymeric emulsifiers is selected from copolymer, AMPS homopolymer and wherein two or more the combination of acrylamide alkyl sulfonic acid and ring N-vinyl carboxylic acid amides.
20. emulsion compositions as claimed in claim 15 is characterized in that, described compositions is substantially free of organic opacifier.
21. a method of protecting skin to exempt from photic damage, described method are included in the described compositions of coating claim 1 on the skin.
22. a method of protecting skin to exempt from photic damage, described method are included in the described compositions of coating claim 15 on the skin.
CNA200610142524XA 2005-10-24 2006-10-23 Compositions comprising polymeric emulsifiers and methods of using the same Pending CN1954797A (en)

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